Multi-element iron-based amorphous alloy material as well as preparation method and application thereof

Abstract

The invention relates to the field of powder metallurgy, in particular to a multi-element iron-based amorphous alloy material and a preparation method and application thereof. The chemical expression of the multi-element iron-based amorphous alloy material is Fe Si B < c > Nb < d > Ni < e > Cr < f > Mo < g >, wherein, the result is 50w; a < lt >; 75, 5lt; blt; 10, 5lt; clt; ct; 15, 1lt; dlt; 5, 1lt; lt, lt; 10, 1lt; flt; 10, 1lt; glt; 5, the sum of a to g being 100. The invention further provides a vacuum gas atomization preparation method of the series of iron-based amorphous powder. The iron-based amorphous alloy powder composed of multiple elements is high in sphericity degree and amorphous content, and can be used as a raw material for preparing surface protection coatings through thermal spraying, laser cladding and other technologies. And the selected alloy elements are moderate in price, and can be used as a surface protection material with corrosion resistance and magnetism.

Description

Technical Field

[0001] The invention relates to the field of powder metallurgy, and in particular to a multi-component iron-based amorphous alloy material and a preparation method and application thereof. Background Art

[0002] Amorphous alloy materials have the characteristics of short-range ordered and long-range disordered atomic arrangement in microstructure, and are uniform and isotropic in macrostructure. These characteristics and features make amorphous alloy materials different from ordinary crystal structure characteristic alloy materials, and they have special physical and chemical properties. For example, in terms of mechanical properties, amorphous alloys have significant performance in strength, toughness, hardness, etc. In addition, amorphous alloys also have excellent wear resistance and corrosion resistance. Therefore, amorphous alloy materials have very broad application prospects.

[0003] Iron-based amorphous alloys are common amorphous alloy materials with the advantages of high strength and hardness, good wear and corrosion resistance, certain magnetic properties, and low cost. In particular, iron-based amorphous alloy coatings have application value in the fields of military, aerospace, marine environmental protection, magnetic shielding, etc. Through the "Navy Advanced Amorphous Coatings" program, the United States applies iron-based amorphous alloy coatings to the surfaces of ships and other equipment. At present, the development of iron-based amorphous coatings mainly lies in two aspects. One is the design of components for the performance required by the application scenario, and the other is the preparation of iron-based amorphous coatings with high amorphous content and low porosity. Iron-based amorphous powder is the raw material for coating preparation and is also the key to determining coating performance. At present, there is an urgent need to provide a multi-element iron-based amorphous alloy powder and a vacuum air atomization preparation method thereof. Summary of the invention

[0004] In order to solve the above technical problems, the present invention provides a multi-component iron-based amorphous alloy material and a preparation method and application thereof.

[0005] In the first aspect, the chemical formula of the multi-component iron-based amorphous alloy material provided by the present invention is: Fe a Si b B c Nb d Ni e Cr f Mo g; wherein, 50 < a < 75, 5 < b < 10, 5 < c < 15, 1 < d < 5, 1 < e < 10, 1 < f < 10, 1 < g < 5, and the sum of a to g is 100. In the present invention, a, b, c, d, e, f, and g respectively represent the atomic mass percentage contents of the corresponding components. The iron-based amorphous alloy powder composed of multiple elements provided by the present invention has a high sphericity and a high amorphous content, and can be used as a raw material for preparing surface protective coatings by technologies such as thermal spraying and laser cladding. Moreover, the alloying elements selected in the present invention have moderate prices and can be used as a surface protective material with both corrosion resistance and magnetism.

[0006] Preferably, 60 < a < 70, 6 < b < 9, 10 < c < 11, 2 < d < 5, 2 < e < 5, 4 < f < 10, 2 < g < 4, and the sum of a to g is 100.

[0007] Preferably, the oxygen content in the multi-element iron-based amorphous alloy material is less than 100 ppm.

[0008] Preferably, the multi-element iron-based amorphous alloy material is in powder form; preferably, the particle size distribution is 10 - 90 μm, and the average particle size is 20 - 40 μm.

[0009] More preferably, the multi-element iron-based amorphous alloy material is spherical powder, with a sphericity greater than 90%, an oxygen content less than 100 ppm, an amorphous content of 91 - 97% for particles with a particle size below 25 μm, an amorphous content of 88 - 91% for particles with a particle size of 25 - 50 μm, an amorphous content of 79 - 88% for particles with a particle size above 50 μm, and a crystallization temperature of 506 - 577 °C.

[0010] In the present invention, by screening the oxygen content and particle size as described above, alloy powder that meets the original design and is suitable for thermal spraying or laser cladding can be obtained better. Furthermore, by screening the sphericity, amorphous content, and crystallization temperature, powder with high fluidity and suitable for preparing amorphous coatings can be obtained better.

[0011] In the second aspect, the present invention provides a preparation method of the multi-element iron-based amorphous alloy material, which is prepared by a vacuum gas atomization method; preferably, it includes surface treatment of the metal raw materials of the alloy components, vacuum melting using a vacuum electromagnetic induction device to obtain a metal liquid; simultaneously spraying the metal liquid and gas for gas atomization; collecting and screening the powder after cooling to obtain the multi-element iron-based amorphous alloy material powder.

[0012] Preferably, the surface treatment includes grinding the metal raw material blocks to remove surface oxides, ultrasonic cleaning in an ethanol or acetone bath to remove surface impurities, and drying at a temperature below 150 °C to prevent oxidation.

[0013] More preferably, the vacuum melting pressure is less than 1.0×10 -5 Pa.

[0014] Preferably, the process further comprises introducing an atomizing gas; preferably, the pressure of the atomizing high pressure gas flow is 6-12 MPa, the atomizing gas is Ar, and the temperature range is 1800-2100°C, preferably 1900-2000°C. During the electromagnetic induction melting process, the vacuum degree of the melting chamber is maintained below 1.0×10 -5 Pa, the introduction of atomizing gas argon helps to reduce oxidation and impurities and ensure the purity of the material. At the same time, the smelting is set in the optimal temperature range, which can melt the metal raw materials better and more evenly, and help improve the smelting efficiency and quality. These conditions work together to ensure the quality and performance of the final product.

[0015] Further preferably, the powder prepared by the gas atomization is cooled and then sieved to obtain an alloy powder with a particle size distribution of 10-90 μm and an average particle size of 20-40 μm. The amorphous powder with a particle size distribution of 10-90 μm and an average particle size range of 20-40 μm provided by the present invention has excellent corrosion resistance and magnetic properties.

[0016] In a third aspect, the present invention provides the use of the above-mentioned multi-component iron-based amorphous alloy material or the multi-component iron-based amorphous alloy material obtained by the above-mentioned preparation method in the preparation of surface protective coatings including thermal spraying technology, laser cladding technology, or the preparation of corrosion-resistant and magnetic surface protective materials.

[0017] The beneficial effects of the present invention are at least as follows: the present invention adopts Fe element as the basic element, and uses Fe, Si, and B as the main components of amorphous powder, that is, iron-silicon-boron alloy as the basis, which has the advantages of high remanence, high coercivity and high magnetic energy product; in addition, Nb is mainly used for solid solution strengthening to improve the strength of the iron-based amorphous alloy; Ni has a certain corrosion resistance while increasing the strength; the addition of Cr can also improve the hardness, corrosion resistance and wear resistance of the alloy; the addition of Mo curbs the chloride ion pitting tendency of the alloy on the one hand, and also increases the remanence and coercivity of the iron-based amorphous alloy on the other hand. The present invention adopts vacuum gas atomization to prepare iron-based amorphous powder, the process is simple, the powder has high yield and sphericity, and the composition is uniform, the oxygen content is low, and it is suitable for spraying and laser cladding to prepare iron-based amorphous alloy coatings. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] In order to more clearly illustrate the technical solutions in the present invention or the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0019] Figure 1 This is a SEM image of the Fe70Si9B11Nb2Ni2Cr4Mo2 amorphous powder of Example 1 of the present invention.

[0020] Figure 2 This is the XRD diagram of the Fe70Si9B11Nb2Ni2Cr4Mo2 amorphous powder of Example 1 of the present invention.

[0021] Figure 3 This is the DSC graph of the Fe70Si9B11Nb2Ni2Cr4Mo2 amorphous powder of Example 1 of the present invention.

[0022] Figure 4 This is a SEM image of the Fe60Si6B10Nb5Ni5Cr10Mo4 amorphous powder of Example 2 of the present invention.

[0023] Figure 5 This is the XRD diagram of the Fe60Si6B10Nb5Ni5Cr10Mo4 amorphous powder of Example 2 of the present invention.

[0024] Figure 6 This is the DSC graph of Fe60Si6B10Nb5Ni5Cr10Mo4 amorphous powder of Example 2 of the present invention.

[0025] Figure 7 This is the SEM image of the Fe65Si8B10Nb3Ni3Cr8Mo3 amorphous powder of Example 3 of the present invention.

[0026] Figure 8 This is the XRD diagram of the Fe65Si8B10Nb3Ni3Cr8Mo3 amorphous powder of Example 3 of the present invention.

[0027] Fig. 9 This is the DSC graph of the Fe65Si8B10Nb3Ni3Cr8Mo3 amorphous powder of Example 3 of the present invention.

[0028] Fig.10 It is a SEM image of Fe78Si5B5Nb2Ni2Cr6Mo2 amorphous powder of comparative example 1 of the present invention.

[0029] Fig.11It is the XRD pattern of the Fe78Si5B5Nb2Ni2Cr6Mo2 amorphous powder of Comparative Example 1 of the present invention.

[0030] Fig.12 It is the DSC pattern of the Fe78Si5B5Nb2Ni2Cr6Mo2 amorphous powder of Comparative Example 1 of the present invention. Detailed implementation manners

[0031] To make the objectives, technical solutions and advantages of the present invention clearer, the technical solutions in the present invention will be clearly and completely described below with reference to the accompanying drawings in the present invention. Obviously, the described embodiments are some, but not all, of the embodiments of the present invention. All other embodiments obtained by those of ordinary skill in the art based on the embodiments in the present invention without making creative efforts shall fall within the protection scope of the present invention.

[0032] For those technical or conditions not specified in the embodiments, they shall be in accordance with the technologies or conditions described in the literature in this field or in accordance with the product specifications. For those instruments without indicating the manufacturer, they are all conventional products that can be obtained through regular channels. The methods are conventional methods unless otherwise specified, and the raw materials can be obtained from public commercial channels unless otherwise specified. For those technical or conditions not specified in the embodiments, they shall be in accordance with the technologies or conditions described in the literature in this field or in accordance with the product specifications.

[0033] An embodiment of the present invention provides a composition of a multi-element iron-based amorphous powder, which includes the following elements: Fe, Si, B, Nb, Ni, Cr, Mo. The spherical shape of the iron-based amorphous alloy powder designed in the embodiment of the present invention is good. At the same time, since it is based on iron, silicon, and boron elements and additional elements such as niobium, nickel, chromium, and molybdenum are added, the coating materials prepared from this series of alloy powders are expected to have high hardness, strong wear and corrosion resistance, and certain magnetic properties. In addition, the cooling rate of the alloy powder prepared by true air atomization is fast, which is easy to form an amorphous structure for the powder. The chemical formula of this alloy is: Fe a Si b B c Nb d Ni e Cr f Mo g ; where a, b, c, d, e, f, g respectively represent the atomic mass percentage contents of the corresponding components, 50 < a < 75, 5 < b < 10, 5 < c < 15, 1 < d < 5, 1 < e < 10, 1 < f < 10, 1 < g < 5, and a + b + c + d + e + f + g = 100. The Fe, Si, B, Nb, Ni, Cr, Mo raw materials used in the embodiments of the present invention are all commercially available bulk raw materials with a purity higher than 99 wt%.

[0034] The embodiment of the present invention provides a method for preparing multi-component iron-based amorphous powder by vacuum gas atomization, comprising subjecting the surface treated raw materials to high-temperature vacuum smelting, and ejecting the obtained molten metal with a high-pressure argon gas flow to achieve atomization, and finally sieving the cooled powder to obtain multi-component iron-based amorphous powder. In an optional embodiment, the gas pressure during the induction smelting process is less than 1.0×10 -5 Pa, the protective gas during the smelting process is argon, and the temperature range is controlled at 1800-2100° C. In an optional embodiment, during the vacuum gas atomization powder making process, the pressure of the high-pressure argon gas flow is 6-12 MPa. In an optional embodiment, the particle size of the multi-component iron-based amorphous powder is selected to be 10-90 μm.

[0035] The following Examples 1-3 are for preparing the appearance, microstructure, glass transition temperature, etc. of multi-component iron-based amorphous powders of Fe70Si9B11Nb2Ni2Cr4Mo2, Fe60Si6B10Nb5Ni5Cr10Mo4, and Fe65Si8B10Nb3Ni3Cr8Mo3.

[0036] Example 1

[0037] The ingredients are calculated by atomic fraction: Fe, 70at.%; Si, 9at.%; B, 11at.%; Nb, 2at.%; Ni, 2at.%; Cr, 4at.%; Mo, 2at.%. The ingredients use industrial materials with a purity of ≥99%, and are first polished with 800-grit sandpaper, ultrasonically cleaned in ethanol for 3 times, each time for 3 minutes, and then dried in a vacuum drying oven at 80°C to prevent oxidation.

[0038] The ingredients are placed in the vacuum electromagnetic induction melting furnace of the vacuum gas atomization powder making device and evacuated to a pressure less than 1.0×10 -5 Pa, and then high-purity argon is introduced to 0.1Pa. The smelting temperature is set to 1900℃ to melt the metal raw materials evenly. The atomization pressure is set to 8MPa. Open the atomization valve and the spray-casting valve to spray out the molten metal and the argon flow at the same time. The metal droplets are quickly cooled in an inert gas environment to form spherical particles. After cooling, the collected granular powder is sieved and vacuum-packed in an inert atmosphere to obtain a multi-element iron-based amorphous powder spherical powder, the powder particle size is 10-88μm, the average particle size is 40μm, the yield is 60%, the sphericity is 96%, and the oxygen content is 55ppm.

[0039] Example 2

[0040] The ingredients are calculated by atomic fraction: Fe, 60at.%; Si, 6at.%; B, 10at.%; Nb, 5at.%; Ni, 5at.%; Cr, 10at.%; Mo, 4at.%. The ingredients use industrial materials with a purity of ≥99%, and are first polished with 800-grit sandpaper, ultrasonically cleaned in ethanol for 3 times, each time for 3 minutes, and then dried in a vacuum drying oven at 80°C to prevent oxidation.

[0041] The ingredients are placed in the vacuum electromagnetic induction melting furnace of the vacuum gas atomization powder making device and evacuated to a pressure less than 1.0×10 -5 Pa, and then high-purity argon is introduced to 0.1Pa. The smelting temperature is set to 1800℃ to melt the metal raw materials evenly. The atomization pressure is set to 6MPa. Open the atomization valve and the spray-casting valve to spray out the molten metal and the argon flow at the same time. The metal droplets are quickly cooled in an inert gas environment to form spherical particles. After cooling, the collected granular powder is sieved and vacuum-packed in an inert atmosphere to obtain a multi-element iron-based amorphous powder spherical powder, the powder particle size is 10-75μm, the average particle size is 25μm, the yield is 75%, the sphericity is 97%, and the oxygen content is 50ppm.

[0042] Example 3

[0043] The ingredients are calculated by atomic fraction: Fe, 65at.%; Si, 8at.%; B, 10at.%; Nb, 3at.%; Ni, 3at.%; Cr, 8at.%; Mo, 3at.%. The ingredients use industrial materials with a purity of ≥99%, and are first polished with 800-mesh sandpaper, ultrasonically cleaned in ethanol for 3 times, each time for 3 minutes, and then dried in a vacuum drying oven at 80°C to prevent oxidation.

[0044] The ingredients are placed in the vacuum electromagnetic induction melting furnace of the vacuum gas atomization powder making device and evacuated to a pressure less than 1.0×10 -5 Pa, and then high-purity argon is introduced to 0.1Pa. The smelting temperature is set to 2100℃ to melt the metal raw materials evenly. The atomization pressure is set to 12MPa. Open the atomization valve and the spray-casting valve to spray out the molten metal and the argon flow at the same time. The metal droplets are quickly cooled in an inert gas environment to form spherical particles. After cooling, the collected granular powder is sieved and vacuum-packed in an inert atmosphere to obtain a multi-element iron-based amorphous powder spherical powder, the powder particle size is 12-90μm, the average particle size is 40μm, the yield is 70%, the sphericity is 97%, and the oxygen content is 39ppm.

[0045] Comparative Example 1

[0046] The same method as in Example 1 is used, except that the ingredients are prepared according to the following ingredients: Fe, 78 at.%, Si, 5 at.%, B, 5 at.%, Nb, 2 at.%, Ni, 2 at.%, Cr, 6 at.%, Mo, 2 at.%. The powder particle size is 5-100 μm, the average particle size is 47 μm, the yield is 55%, the sphericity is 92%, and the oxygen content is 80 ppm.

[0047] The relevant performance tests were carried out on the powders prepared in each example, and the data are summarized in Table 1.

[0048] Table 1 Amorphous content data of multi-component Fe-based amorphous powders prepared in various examples.

[0049]

[0050] Combined with Table 1 and Figure 1-12 It can be seen that the multi-component Fe-based amorphous alloy powder prepared by the gas atomization method of the present invention has high sphericity and can be used as a raw material in laser cladding, thermal spraying and other industries.

[0051] In summary, the multi-component iron-based amorphous alloy powder and the preparation method thereof described in the present invention can directly prepare iron-based amorphous alloy powder with high sphericity and high amorphous content by vacuum gas atomization, and can be applied to laser cladding, thermal spraying and other technologies to prepare surface protective coatings.

[0052] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A multi-component iron-based amorphous alloy material, characterized in that: The chemical formula of the multi-component iron-based amorphous alloy material is: Fe a Si b B c Nb d Ni e Cr f Mo g ; where 50 < a < 75, 5 < b < 10, 5 < c < 15, 1 < d < 5, 1 < e < 10, 1 < f < 10, 1 < g < 5, and the sum of a to g is 100.

2. The multi-component iron-based amorphous alloy material according to claim 1, characterized in that: 60 < a < 70, 6 < b < 9, 10 < c < 11, 2 < d < 5, 2 < e < 5, 4 < f < 10, 2 < g < 4, and the sum of a to g is 100.

3. The multi-component iron-based amorphous alloy material according to claim 1 or 2, characterized in that: The oxygen content in the multi-component iron-based amorphous alloy material is less than 100 ppm.

4. The multi-component iron-based amorphous alloy material according to any one of claims 1 to 3, characterized in that: The multi-component iron-based amorphous alloy material is in powder form; preferably, the particle size distribution is 10 - 90 μm, and the average particle size is 20 - 40 μm.

5. The multi-component iron-based amorphous alloy material according to claim 4, characterized in that: The multi-component iron-based amorphous alloy material is spherical powder, with a sphericity greater than 90%, an oxygen content less than 100 ppm, the amorphous content of particles with a particle size below 25 μm being 91 - 97%, the amorphous content of particles with a particle size of 25 - 50 μm being 88 - 91%, the amorphous content of particles with a particle size above 50 μm being 79 - 88%, and the crystallization temperature being 506 - 577 °C.

6. The method for preparing the multi-component iron-based amorphous alloy material according to any one of claims 1 to 5, characterized in that: Prepared by the vacuum gas atomization method; including surface treatment of the metal raw materials of the alloy components, vacuum melting using a vacuum electromagnetic induction device to obtain molten metal; spraying the molten metal and gas simultaneously for gas atomization; and screening after cooling to obtain the multi-component iron-based amorphous alloy material powder.

7. The preparation method according to claim 6, characterized in that: The surface treatment includes grinding the bulk of the metal raw materials, ultrasonic cleaning in an ethanol or acetone bath, and drying at a temperature below 150 °C.

8. The preparation method according to claim 6 or 7, characterized in that: The vacuum melting pressure is less than 1.0×10 -5 Pa; and / or, further comprising introducing an atomizing gas; preferably, the pressure of the atomizing high-pressure airflow is 6-12 MPa, the atomizing gas is Ar, and the temperature ranges from 1800-2100°C.

9. The preparation method according to any one of claims 6 to 8, characterized in that: The powder obtained by gas atomization preparation is screened after cooling to obtain an alloy powder with a particle size distribution of 10 - 90 μm and an average particle size of 20 - 40 μm.

10. The application of the multi-component iron-based amorphous alloy material according to any one of claims 1 - 5 or the multi-component iron-based amorphous alloy material obtained by the preparation method according to any one of claims 6 - 9 in preparing a surface protection coating by thermal spraying technology, preparing a surface protection coating by laser cladding technology, or preparing a corrosion-resistant and magnetic surface protection material.

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